Polycyclic dyes

ABSTRACT

The present invention relates to a process for the preparation of certain polycyclic dyes and in particularly the preparation of a polycyclic dye of Formula I: ##STR1## By reacting a phenyltartronic acid of Formula II: ##STR2## With either a compound of Formula III: ##STR3## or a compound of Formula IV: ##STR4##

This is a division of application Ser. No. 410,630, filed Sep. 21, 1989,now U.S. Pat. No. 5,084,580.

This specification describes an invention relating to a process for thepreparation of certain polycyclic dyes.

According to the present invention there is provided a process for thepreparation of a polycyclic dye of the Formula I: ##STR5## by reacting aphenyltartronic acid of Formula II: ##STR6## wherein W is --NR¹ R² or--OR³ ;

R³ is H or an optionally substituted alkyl, alkenyl, cycloalkyl oraralkyl group;

R¹ & R² each independently is H, or an optionally substituted alkyl,alkenyl, cycloalkyl, aralkyl or aryl group; or

R¹ & R² together with the nitrogen atom to which they are attached forma heterocyclic ring; or

R¹ or R² together with the nitrogen atom and the adjacent carbon atom ofRing B form a heterocyclic ring; and

Ring B is unsubstituted, apart from the group W, or is substituted byone or two further groups;

with either (a) a compound of the Formula III: ##STR7## wherein, Z¹ & Z²each independently is --O--, --S-- or --NY-- in which Y is H, anoptionally-substituted hydrocarbon group or an acyl group;

X¹ & X² each independently is H, halogen, cyano, alkyl, aryl, carbamoyl,sulphamoyl, COOH or carboxylic acid ester; &

Ring A is unsubstituted or is substituted by from one to three groups;

or (b) a compound of the Formula IV: ##STR8## wherein Z¹, Z², X¹ and X²are as hereinbefore defined; and oxidation of the intermediate compoundto dehydrogenate the peripheral heterocyclic rings.

The optionally substituted hydrocarbon group represented by Y ispreferably C₁₋₈ -alkyl, and more preferably C₁₋₄ -alkyl, or monocyclicaryl, more preferably phenyl. The acyl group represented by Y ispreferably C₁₋₄ -alkyl- or monocyclic-aryl-carbonyl or -sulphonyl whichmay be substituted by one or more groups selected from hydroxy, halogen,nitrogen, C₁₋₄ -alkyl and C₁₋₄ -alkoxy. Examples of the optionallysubstituted hydrocarbon groups represented by Y are alkyl and preferablyC₁₋₄ -alkyl, such as methyl, ethyl, n-propyl and iso-propyl; substitutedalkyl, preferably substituted C₁₋₄ -alkyl, such as beta-hydroxyethyl,beta-methoxyethyl and beta-ethoxyethyl; phenyl and substituted phenylsuch as tolyl, chlorophenyl, nitrophenyl and C₁₋₄ -alkoxyphenyl.Examples of the acyl groups represented by Y are acetyl, propionyl,n-butyryl, iso-butyryl, benzoyl and nitrobenzoyl, chlorobenzoyl,methylbenzoyl, methoxybenzoyl and hydroxybenzoyl.

The aryl group represented by X¹ or X² is preferably mono-homocyclicaryl, that is phenyl and substituted phenyl. The C₁₋₄ -alkyl and alkoxygroups represented by X¹ or X² may also be substituted and suitablesubstituents for these and the aryl group are hydroxy, halogen, nitro,C₁₋₄ -alkyl and C₁₋₄ -alkoxy. The halogen represented by X¹ or X² ispreferably chlorine or bromine.

The carbamoyl and sulphamoyl groups represented by X¹ or X² arepreferably of the formula --CONL¹ L² or --SO₂ NL¹ L² wherein L¹ and L²are each independently hydrogen, C₁₋₄ -alkyl or monocyclic aryl,preferably phenyl. The carboxylic acid ester groups represented by X¹and X² are preferably of the formula --COOL³ wherein L³ is optionallysubstituted alkyl, especially C₁₋₄ -alkyl, or monocyclic aryl,especially phenyl, in which the substituents are as defined above.

When any of R¹ to R³ is alkyl or alkenyl it preferably contains up to20, more preferably up to 10 carbon atoms and especially up to 4, carbonatoms, with a preferred minimum of 3 carbon atoms for alkenyl groups);when cycloalkyl it is preferably C₄₋₈ -cycloalkyl, such as cyclohexyl;and when aryl or aralkyl, the aryl is preferably monohomocyclic aryl,i.e. phenyl, and the aralkyl is preferably phenyl-C₁₋₄ -alkylene, suchas benzyl and phenylethyl. Where the groups represented by R¹ to R³ aresubstituted, examples of preferred substituents are alkyl, alkoxy,nitro, halogen, alkoxyalkoxy, cyclohexyl, phenyl, diphenyl, hydroxy,alkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyloxy,alkoxyalkoxycarbonyloxy, alkylcarbonyloxy, cyano and amino in which eachalkyl is preferably C₁₋₄ -alkyl, Where the groups represented by R¹ andR², together with the nitrogen atom to which they are attached, form aheterocyclic group this is preferably alicyclic, such as piperidino ormorpholino. Where a group represented by R¹ or R² together with thenitrogen atom to which it is attached and an adjacent carbon atom ofRing B or Ring A form a heterocyclic group fused to Ring B or Ring Arespectively, this is preferably a 6-membered heteroaliphatic ring, i.e.R¹ or R² is trimethylene, and the combined fused rings preferably form atetrahydroquinolyl group.

It is preferred that the compound of Formula I is "unsymmetrical" byvirtue of differences in the definitions of Z¹ and Z², X¹ and X² and/orRing A and Ring B, because lack of symmetry generally gives rise to animprovement in dyeing performance, especially in build-up on the fibre.However, it is generally preferred that Z¹ and Z² are identical and X¹and X² are identical and that the lack of symmetry arises fromdifferences in Rings A and B. Where Ring A and Ring B are different, thedifference preferably lies in the nature and/or the number ofsubstituents carried by each ring. The difference lies preferably in theidentity of the groups R¹ to R³ but may lie in the identity and/or thenumber of the substituents carried by the rings. Examples of furthersubstituents for Ring B, in addition to the group W, are alkyl; alkenyl;alkoxy; alkoxyalkoxy; alkoxycarbonyalkoxy; alkoxyalkoxycarbonylalkoxy;alkylcarbonyloxyalkoxy; cyanoalkyoxy, hydroxyalkoxy; halogen, especiallychlorine or bromine; hydroxy; alkylthio; arylthio; aryloxy; alkylcarbonyand alkylsulphonyl; and especially such groups in which the alkyl oralkenyl contains up to 4 carbon atoms and the aryl is phenyl. Examplesof substituents for Ring A, is addition to those listed above for RingB, are NR¹ R², OR³ and NHacyl, especially NCOC₁₋₄ -alkyl and --NHSO_(2C)₁₋₄ -alkyl.

It is preferred hat X¹ and X² are both hydrogen and also preferred thatZ¹ and Z² are both oxygen. When both these pairs of groups areidentical, the preferred asymmetry in the compound of Formula I isprovided by differences in Rings A and B. By this is meant that there iseither a different number or different pattern of substituents on eachring.

The present process may be performed by heating the reactants in a meltbut preferably in an acidic medium, preferably an organic acid, adespecially an alkanecarboxylic acid such as acetic acid, propionic acidor butyric acid.

It is preferred to perform the process in which W is OR³ in the presenceof a strong acid catalyst, especially H₂ SO₄. However, where W is NR¹ R²such a catalyst is not generally required and is believed to have anadverse effect on the process.

The process is preferably performed at a temperature from 50° C. to 100°C., especially 70° C. to 100° C., where a solvent is present,conveniently under reflux. Reaction is preferably contained until allthe starting materials are consumed which can take up to 25 hours.

Further reactions to the dyes in which any or all of R¹, R² and R³ are Hwith alkylating, arylating or acylating agents permits the preparationof a wide range of substituted hydroxy and amino (secondary and tertiaryamino) groups.

The final oxidation step may be effected by any convenient oxidisingagent for dehydrogenating a carbon-carbon single bond, such as apersulphate or hydrogen peroxide.

The compound of Formula III, in which Ring A also carries a group NR¹R², may be prepared by the reaction of an aminomandelic acid (in whichthe amino group is protected, if necessary, by acylation) with ahydroquinone in accordance with the procedures described in GB2,068,402A.

According to a further feature of the present invention there isprovided a process for the preparation of a compound according toFormula III in which Ring A carries a group NR¹ R² in the 4-positionwhich comprises reacting a mandelic acid of the Formula V: ##STR9##wherein A has the same meaning as in Formula I with a compound of theFormula VI: ##STR10## wherein X¹ and X² have the same meanings as inFormula I. it is preferred that, in Formula VI, X¹ and X² are bothhydrogen.

This reaction is conveniently performed in an acidic medium in thepresence of a strong acid catalyst as described above for thepreparation of the compound of Formula I but at a lower temperature inthe range 40° C. to 80° C. especially from 49° C. to 75° C.

The present process is especially suitable for the preparation ofcompounds of Formula I in which:

(a) Ring B carries a group, NR¹ R², and both rings, optionally, carryone or more other substituents; or

(b) Rings A and B both carry a group, NR¹ R², which may be the same ordifferent, and, optionally, one or more other substituents.

Compounds of Formula I in which W is NR¹ R², Ring B carries a methylgroup adjacent to NR¹ R² and Ring A is unsubstituted or substituted inthe 4-position by an alkyl or alkoxy group give blue shades when appliedto synthetic fibres, especially polyesters by disperse dyeing processes,and build up well to give navy shades and such compounds form a featureof the present invention.

According to a further feature of the present invention there isprovided a compound of the formula: ##STR11## wherein X¹ & X² eachindependently is H, cyano, alkyl, aryl, carbamoyl, sulphamoyl, COOH orcarboxylic acid ester;

Z¹ & Z² each independently is --O--, --S-- or --NY-- in which Y is H, anoptionally-substituted hydrocarbon group or an acyl group;

R¹ & R² each independently is H or an optionally substituted alkyl,alkenyl, cycloalkyl, aryl or aralkyl group; or

R¹ & R² together with the N atom to which they are attached, form aheterocycle;

R⁴ & R⁵ each independently is H, halogen or an optionally substitutedalkyl, alkenyl or alkoxy group; or

R¹ & R⁴ together with the N atom and the two carbon atoms in Ring B towhich they are attached form a heterocycle fused to Ring B; or

R² & R⁵ together with the N atom and the two carbon atoms in Ring B towhich they are attached form a heterocycle fused to Ring B;

R⁶ is H, halogen or an optionally substituted alkyl or alkoxy group or agroup NR¹ R² in which each of R¹ and R² is as hereinbefore defined;

R⁷ & R⁸ each independently is H, halogen or an optionally substitutedalkyl, alkenyl or alkoxy group; or

R¹ & R⁷ together with the N atom and the two carbon atoms in Ring A towhich they are attached form a heterocycle fused to Ring A; or

R² & R⁸ together with the N atom and the two carbon atoms in Ring A towhich they are attached form a heterocycle fused to Ring A;

and where R⁶ is NR¹ R² this may be the same as or different from the NR¹R² group present in Ring B.

It is preferred that the compound of Formula VII is "unsymmetrical byvirtue of differences in the definitions of Z¹ and Z², X¹ and X² and/orthe number and pattern of substituents on Ring A and Ring B, becauselack of symmetry generally gives rise to an improvement in dyeingperformance, especially in build-up on the fibre. It is preferred thatX¹ and X² are the same and preferably H. It is also preferred that Z¹and Z² are the same and preferably oxygen. Where X¹ and X² are identicaland Z¹ and Z² are identical it is preferred that the lack of symmetryarises from a difference in the number or pattern of substituents onRing A and Ring B.

Preferences for the groups represented by X¹, X², Z¹ and Z² are the sameas for the same groups in Formula I

In Ring A it is preferred that R⁶ is independently selected from H,halogen, C₁₋₁₀ -alkyl, C₃₋₁₀ -alkenyl, C₁₋₁₀ -alkoxy and NR¹ R², inwhich each of R¹ and R² is independently H; C₁₋₆ -alkyl, more especiallyC₁₋₄ -alkyl; or C₁₋₄ -alkyl substituted by a group selected from alkoxy,alkoxyalkoxy, hydroxy, cyano, halogen especially chlorine or bromine,phenyl, alkoxycarbonyl, alkoxyalkoxycarbonyl and alkylcarbonyloxy inwhich all the alkyl groups preferably contain up to 4 carbon atoms.Alternatively either R¹ and R⁷ or R² and R⁸, together with the N atom towhich R¹ or R² is attached and two carbon atoms in Ring A, may form apiperidine ring fused to Ring A or R¹ and R², together with the N atomto which they are attached, may form a pendant mono or bicyclicheterocyclic group, especially piperidino or morpholino, attached toRing A through the N atom. Where R⁶ is not NR¹ R², it is preferred thateach of R⁷ and R⁸ is H.

In Ring B it is preferred that each of R¹ and R² independently is H;C₁₋₆ -alkyl, more especially C₁₋₄ -alkyl; or C₁₋₄ -alkyl which isoptionally substituted by a group selected from alkoxy, alkoxyalkoxy,hydroxy, cyano, halogen especially chlorine or bromine, phenyl,alkoxycarbonyl, alkoxycarbonyloxy, alkoxyalkoxycarbonyl andalkylcarbonyloxy in which all the alkyl groups preferably contain up to4 carbon atoms; or that either R¹ and R⁴ or R² and R⁵, together with theN atom to which R¹ or R² is attached and two carbon atoms in Ring B,form a piperidine ring fused to Ring B; or that R¹ and R²,together withthe N atom to which they are attached, form a pendant mono or bicyclicheterocyclic group, especially piperidino or morpholino, attached toRing B through the N atom. It is preferred that at least one of R⁴ andR⁵ is other than hydrogen and, especially, an alkyl or alkoxy group ashereinafter more specifically defined.

The alkyl group represented by R⁴, R⁵, R⁶, R⁷ or R⁸ is preferably C₁₋₄-alkyl, especially methyl or ethyl. The alkenyl group represented by R⁴,R⁵, R⁶, R⁷ or R⁸ is preferably C₃₋₄ -alkenyl, especially allyl. Thealkoxy group represented by R⁴, R⁵, R⁶, R⁷ or R⁸ is preferably anunsubstituted C₁₋₁₀ -alkoxy or a C₁₋₄ -alkoxy group which is substitutedby a group selected from alkoxy, hydroxy, alkylcarbonyloxy,alkoxyalkoxycarbonyl, alkoxycarbonyl, halogen and cyano, in which allthe alkyl groups preferably contain up to 4 carbon atoms. The halogenrepresented by R⁴, R⁵, R⁶, R⁷ or R⁸ is preferably chlorine or bromine.

In one preferred sub-class of the compound of Formula VII, X¹, X² and R¹are H; Z¹ and Z² are oxygen; R² is H or C₁₋₄ -alkyl; R⁴, R⁵, R⁷ and R⁸each independently is H, C₁₋₄ -alkyl or C₁₋₁₀ -alkoxy, more especiallyC₁₋₄ -alkoxy; and R⁶ is NH₂. The dyes of this preferred sub-class offormula VII, generally give reddish-blue to turquoise shades onpolyester textile materials with excellent fastness properties,especially heat and wet fastness. Specific examples of such dyes are:

                  TABLE 1                                                         ______________________________________                                        R.sup.1                                                                              R.sup.2 R.sup.4  R.sup.5                                                                              R.sup.6                                                                             R.sup.7                                                                             R.sup.8                            ______________________________________                                        H      H       CH.sub.3 H      NH.sub.2                                                                            H     H                                  H      H       OCH.sub.3                                                                              H      NH.sub.2                                                                            H     H                                  H      H       Cl       H      NH.sub.2                                                                            H     H                                  H      H       C.sub.2 H.sub.5                                                                        H      NH.sub.2                                                                            H     H                                  H      H       CH.sub.3 CH.sub.3                                                                             NH.sub.2                                                                            H     H                                  ______________________________________                                    

In another preferred sub-class of the compound of Formula VII, X¹, X²,R¹, R⁵, R⁷ and R⁸ are H; Z¹ and Z² are oxygen; R² is C₁₋₄ -alkyl; R⁴ isC₁₋₄ -alkyl or C₁₋₁₀ -alkoxy, more especially C₁₋₄ -alkoxy; and R⁶ is H,C₁₋₄ -alkyl or C₁₋₄ -alkoxy. The dyes of this preferred sub-class ofFormula VII build up strongly on polyester textile materials to givestrong navy shades with excellent fastness properties, especially heatand wet fastness. Specific examples of such dyes are:

                  TABLE 2                                                         ______________________________________                                        R.sup.1                                                                              R.sup.2  R.sup.4    R.sup.5                                                                            R.sup.6                                                                              R.sup.7                                                                            R.sup.8                           ______________________________________                                        H      H        CH.sub.3   H    H      H    H                                 H      H        CH.sub.3   H    CH.sub.3                                                                             H    H                                 H      H        C.sub.2 H.sub.5                                                                          H    OC.sub.3 H.sub.7                                                                     H    H                                 H      H        n-C.sub.3 H.sub.7                                                                        H    C.sub.3 H.sub.7                                                                      H    H                                 H      H        OCH.sub.3  H    H      H    H                                 H      H        OC.sub.2 H.sub.5                                                                         H    OC.sub.3 H.sub.7                                                                     H    H                                 H      H        O-n-C.sub. 3 H.sub.7                                                                     H    OC.sub.3 H.sub.7                                                                     H    H                                 H      C.sub.2 H.sub.5                                                                        CH.sub.3   H    H      H    H                                 ______________________________________                                    

Examples of other dyes according to Formula VII are:

                                      TABLE 3                                     __________________________________________________________________________    R.sup.1                                                                            R.sup.2  R.sup.4                                                                           R.sup.5                                                                          R.sup.6   R.sup.7                                                                          R.sup.8                                                                         X.sup.1                                   __________________________________________________________________________    H    C.sub.2 H.sub.5                                                                        H   H  NH.sub.2  H  H H                                         H    C.sub.2 H.sub.5                                                                        CH.sub.3                                                                          H  NH.sub.2  H  H H                                         H    C.sub.3 H.sub.5                                                                        H   H  NH.sub.2  H  H H                                         H    i-C.sub.3 H.sub.7                                                                      CH.sub.3                                                                          H  NH.sub.2  H  H H                                         H    s-C.sub.4 H.sub.9                                                                      H   H  NH.sub.2  H  H H                                         H    C.sub.2 H.sub.4 COOH                                                                   H   H  NH.sub.2  H  H H                                         --CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --                                               H   H  NH.sub.2  CH.sub.3                                                                         H H                                         --CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --                                               H   H  NH.sub.2  H  H H                                         --CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --                                               H   H  N(EtCOOEtOEt).sub.2                                                                     H  H H                                         H    H        C.sub.2 H.sub.5                                                                   H  NH.sub.2  CH.sub.3                                                                         H H                                         --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --                                           H   H  NH.sub.2  H  H H                                         H    --CH.sub.2 CH.sub.2 CH.sub.2 --                                                            H  NH.sub.2  H  H H                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                        H   H  N(C.sub.2 H.sub.5).sub.2                                                                H  H H                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                        H   H  N(C.sub.2 H.sub.5).sub.2                                                                H  H CH.sub.3                                  H    H        CH.sub.3                                                                          CH.sub.3                                                                         NH.sub.2  CH.sub.3                                                                         H H                                         C.sub.2 H.sub.4 CN                                                                 C.sub.2 H.sub.4 COOCH.sub.3                                                            H   H  OC.sub.3 H.sub.7                                                                        H  H H                                         CH.sub.3                                                                           CH.sub.3 H   H  NH.sub.2  H  H H                                         H    C.sub.2 H.sub.4 OH                                                                     CH.sub.3                                                                          H  NH.sub.2  H  H H                                         H    s-C.sub.4 H.sub.9                                                                      CH.sub.3                                                                          H  NH(s-C.sub.4 H.sub.9)                                                                   H  H H                                         __________________________________________________________________________

In Table 3 and subsequent tables

This invention is further illustrated by the following examples in whichall parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1

A mixture of 2.84 g of5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzofuran, 4.8 g of4-amino-3-methyl-phenyltartronic acid (as the dipotassium salt) and 50ml of glacial acetic acid was stirred under reflux for 18 hours. At theend of this period 2.5 g of ammonium persulphate was added and heatingcontinued for a further 1 hour. After cooling to ambient theprecipitated solid was filtered, washed acid-free with water, thenmethanol, and dried.

A mixture of 3.6 g of this product in 110 ml of 70% sulphuric acid washeated at 95° C. for 7 hours. After cooling, this mixture was drownedinto 1 liter of water and the crude product,3-(4-aminophenyl)-7-(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran, isolated by filtration. This was then extracted intopyridine, screened and the solvent removed under vacuum. The productdissolved in pyridine to give a blues solution with an absorptionmaximum at 657 nm.

When applied to the polyester material from an aqueous dispersion itgave a bright mid-blue shade with excellent heat and wet fastnessproperties and it also built up well.

The 5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzofuran usedin this Example was prepared by stirring 21 g of 4-acetylaminomandelicacid and 11 of hydroquinone in 95 ml of glacial acetic acid and 5 ml100% sulphuric acid at 55° C. for 21 hours, cooling to ambient anddrowning into 1 liter of water. The precipitate was isolated byfiltration, washed acid-free with water and dried.

EXAMPLE 2

The procedure of Example 1 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 3.2 g of4-N-ethylaminophenyltartronic acid to give3-(4aminophenyl)-7-(4-N-ethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran. This dissolved in pyridine to give a blue solutionhaving an absorption maximum of 667 nm.

When applied to polyester from an aqueous dispersion it gave a brightblue shade with very high heat fastness and excellent wash andperspiration fastness.

EXAMPLE 3

The procedure of Example 1 was repeated except that in place of the 4.8g of 4-amino-3-methylphenyltartronic acid there were used 4.7 g of3-methyl-4-N-ethylaminophenyltartronic acid to give3-(4-amino-phenyl)-7-(3-methyl-4-N-ethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran. This dissolved in pyridine to give a greenish-bluesolution having an absorption maximum at 672 nm.

When applied to a polyester textile material form an aqueous dispersionit gave a greenish blue shade having good fastness to wet treatment andit built up well.

EXAMPLE 4

The procedure of Example 1 was repeated except that in place of the 4.8g of 4-amino-3-methylphenyltartronic acid there were used 4.6 g of4-amino-3-methoxyphenyltartronic acid to give3-(4-aminophenyl)-7-(4-amino-3-methoxyphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2b,4:5-b']difuran.

When applied to a polyester textile material from an aqueous dispersionit gave a greenish-blue shade with high heat fastness and very goodperspiration and wash fastness.

EXAMPLE 5

The procedure described in Example 1 was repeated except that in placeof the 4.8 g of 4-amino-3-methylphenyltartronic acid there were used 5.0g of 4-amino-3-chlorophenyltartronic acid to give3-(4-aminophenyl)-7-(4-amino-3-chlorophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran. This dissolved in pyridine to give a blue solutionhaving an absorption maximum at 645 n.

When applied to a polyester textile material from an aqueous dispersionit gave a reddish blue shade with good fastness to wet treatments.

EXAMPLE 6

The procedure of Example 1 was repeated except that in place of the 4.8g of 3-amino-4-methylphenyltartronic acid there were used 5.4 g of4-beta-carboxyethylaminophenyltartronic acid to give3-[4-aminophenyl)-7-(4-beta-carboxyethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran. A portion of this product (1.3 g) was esterified bystirring and boiling under reflux for 5 hours in a mixture of 75 ml ofmethanol and 7.5 ml of concentrated sulphuric acid to give3-(4-aminophenyl)-7-(4-beta-carbomethoxyethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b, 4:5-b']difuran. This dissolved inpyridine to give a blue solution having an absorption maximum at 656 nm.

When applied to polyester textile material from an aqueous dispersion itgave a bright blue shade with good fastness properties.

EXAMPLE 7

The procedure of Example 1 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 4.7 g of4-N-allylaminophenyltartronic acid to give3-(4-aminophenyl)-7-(4-N-allylaminopheny)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran. This dissolved in pyridine to give a blue solutionhaving an absorption maximum at 663 nm.

When applied to polyester from an aqueous dispersion it gave a brightblue shade with good build up and high fastness to heat and washtreatments.

EXAMPLE 8

The procedure of Example 1 was repeated except that the 2.84 g of5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzo- furan wasreplaced by 2.26 g of 5-hydroxy-2-oxo-3-phenyl-2,3-dihydro- benzofuranto give3-phenyl-7-(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-,4:5-b']difuran. This dissolved in pyridine to give a blue solutionhaving an absorption maximum at 620 nm.

When applied to polyester form an aqueous dispersion it built up well togive a navy blue shades with good fastness to heat and wash treatments.

EXAMPLE 9

The procedure of Example 1 was repeated except that the 2.84 g of5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzo- furan wasreplaced by 3.0 g of5-hydroxy-2-oxo-3-(3-methyl-4-acetylaminophenyl)-2,3-dihydrobenzofuranand the 4.8 g of 4-amino-3-methylphenyltartronic acid by 4.8 g4-morpholinophenyltartronic acid. The product,3-(3-methyl-4-aminophenyl)-7-(4-morpholinophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue solution having anabsorption maximum at 655 nm.

When applied to polyester from an aqueous dispersion it gives brightblue shades with good heat fastness and wash treatments.

The 5-hydroxy-2-oxo-3(3-methyl-4-acetylaminophenyl)-2,3-hydrobenzofuranused in this Example was prepared by stirring 14 g of3-methyl-4-actylaminomandelic acid with 6.9 g of hydroquinone in 95 mlof acetic acid and 5 ml of 100% sulphuric acid at 80° C. for 12 hours,cooling to ambient temperature and drowning into 1 liter of water. Theprecipitate was isolated by filtration, washed acid-free with water anddried.

EXAMPLE 10

The procedure of Example 9 was repeated except that in place of the 4.8g of 4-morpholinophenyltartronic acid there was used 4.0 g of4-amino-3-ethylphenyltartronic acid. The product,3-(3-methyl-4-aminophenyl)-7-(3-ethyl-4-aminophenyl)-2,6-dioxo-2,6-dihdyrobenzo[1:2-b,4:5-b'[difuran, dissolves in pyridine to give a blue solution having anabsorption maximum at 660 nm.

When applied to polyester from aqueous dispersion it gives bright blueshades with good fastness to heat and wash treatments.

EXAMPLE 11

The procedure of Example 1 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 3.9 g of4-N-isopropylamino-3-methylphenyltartronic acid. The product,3-(4-aminophenyl)-7-(4-isopropylamino-3-methylphenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue solution having anabsorption maximum at 655 nm.

When applied to polyester form aqueous dispersions it gives bright blueshades with good wet fastness and good heat fastness.

EXAMPLE 12

The procedure of Example 1 was repeated except that in place of the 4.8g of 4-amino-3-methylphenyltartronic acid there was used 3.5 g of4-N-sec-butylaminophenyltartronic acid. The product,3-(4-aminophenyl)-7-(4-sec-butylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue solution having anabsorption maximum at 676 nm.

When applied to polyester it gives blue shades with good heat and wetfastness.

EXAMPLE 13

The procedure of Example 1 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 3.6 g of4-piperidinophenyltartronic acid. The product,3-(4-aminophenyl)-7-(4-piperidinophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue solution having anabsorption maximum at 664 nm.

When applied to polyester materials it gives blue shades with goodfastness to heat and wet treatments.

EXAMPLE 14

The procedure of Example 1 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 3.6 g of1,2,3,4-tetrahydroquinolin-6-yltartronic acid. The product,3-(4-aminophenyl)-7-(1,2,3,4-tetrahydroquinolin-6-yl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran, dissolves in pyridine to give a blue solution having anabsorption maximum at 678 nm.

When applied to polyester materials from aqueous dispersion it givesblue shades with good heat and wet fastness.

EXAMPLE 15

A mixture of 0.62 g of 4-methylaminophenol, 4.4 g of4-diethylaminophenyltartronic acid (as the dipotassium salt) and 25 mlof glacial acetic acid was stirred under reflux for 5 hours. 1.14 g ofammonium persulphate was then added and heating continued for 1 hour.After cooling to ambient temperature, 25 ml of water was added and theproduct,3,7-di(4-diethylaminophenyl)-2,6-dioxo-5-methyl-2,6-dihydro-5H-furo[2:3-f]indole,isolated by filtration. It dissolves in chloroform to give greenish bluesolutions having an absorption maximum at 676 nm.

When applied to polyester materials it gives greenish blue shades withgood wet and heat fastness.

EXAMPLE 16

In place of the 0.62 g of 4-methylaminophenol used in Example 15 therewas used 0.62 g of 2-methylhydroquinone. The product,3,7-di(4-diethylaminophenyl)-4-methyl-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran, dissolves in chloroform to give a greenish blue solutionhaving an absorption maximum at 685 nm.

When applied to polyester materials it gives greenish blue shades withgood fastness to heat and wet treatments.

EXAMPLE 17

1.0 g of the product obtained as in Example 1 was dissolved in a mixtureof 25 ml of methylethylketone and 10 ml of acetic acid. 1.0 g of sodiumborohydride was added portionwise, the temperature rising to 50° C.After stirring for 1 hour a further 1.0 g of sodium borohydride wasadded the temperature again rising to 50° C. After 15 minutes thereaction was complete as judged by TLC.

The reaction mixture was poured into 250 ml water and the precipitatedproduct,3-(4-sec-butylaminophenyl)-7-(4-sec-butylamino-3-methylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran, isolated by filtration, washing with water and drying.It dissolves in pyridine to give a greenish-blue solution having anabsorption maximum at 695 nm.

When applied to polyester materials from aqueous dispersion it givesgreenish-blue shades with good heat and wet fastness.

EXAMPLE 18

The procedure of Example 1 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 5.0 g of4-beta-hydroxyethyl-3-methylphenyltartronic acid to give3-(4-aminophenyl)-7-(4-beta-hydroxyethylamino-3-methylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b']difuran. This dissolved in pyridine to give a blue solutionhaving an absorption maximum at 670 nm.

When applied to polyester materials from aqueous dispersion it gave blueshades with good heat and wet fastness.

EXAMPLE 19

The procedure of Example 1 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 4.6 g of4-amino-3,5-dimethylphenyltartronic acid to give3-(4-aminophenyl)-7-(4-amino-3,5-dimethylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran. It dissolves in pyridine to give a blue solution havingan absorption maximum at 662 nm.

When applied to polyester materials it gave blue shades with good heatand wet fastness.

EXAMPLE 20

The procedure of Example 1 was repeated except that the 2.84 g of5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzo- furan wasreplaced by 2.84 g of5-hydroxy-2-oxo-3(4-n-propoxyphenyl)-2,3-dihydrobenzofuran to give3-(4-n-propoxyphenyl)-7-(4-amino-3-methylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran. It dissolves in pyridine to give a reddish-blue solutionhaving an absorption maximum at 620 nm.

When applied to polyester materials it builds up to give navy blueshades with good heat and wet fastness.

EXAMPLE 21

The procedure of Example 9 was repeated except that the 3.0 g of5-hydroxy-2-oxo-3(3-methyl-4-acetylaminophenyl)-2,3-dihydrobenzofuranwas replaced by 2.84 g of5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzofuran to give3-(4-aminophenyl)-7-(4-morpholinophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran. This dissolves in ethyl acetate to give a blue solutionhaving an absorption maximum at 618 nm.

When applied to polyester materials it gives reddish-blue shades withgood heat and wet fastness.

EXAMPLE 22

1 g of the product obtained from Example 21 was added to a mixture of 50ml of acrylic acid and 3.2 ml water and the mixture stirred at 70°-75°C. for 3 hours. After cooling to ambient temperature, 85 ml of water wasadded and the product isolated by filtration, washing with water anddrying.

It was then added to a mixture of 20 ml of 2-ethoxyethanol and 1 ml of100% sulphuric acid and heated at 70-80° C. for 4 hours. After coolingthe mixture was added to water (200 ml). The product3-(4-(bis-[2-(2-ethoxyethoxycarbonyl)ethyl]aminophenyl)-7-(4-morpholinophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran isolated by filtration, washed with water and dried. Itdissolves in pyridine to give a bleu solution having an absorptionmaximum at 665 nm.

When applied to polyester textile materials it gives blue shades withgood heat and wet fastness.

EXAMPLE 23

A mixture of 2.26 g of 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran,3.0 go of 4-hydroxyphenyltartronic acid (as the dipotassium salt), 23.75ml of glacial acetic acid and 1.25 of concentrated sulphuric acid wasstirred under reflux for 12 hours. After the addition of 2.2 g ammoniumpersulphate heating continued for 1 hour and cooled to ambienttemperature. The cool mixture was added to 250 ml water and the product,3-phenyl-7-(4-hydroxyphenyl)-2,6-dioxo- 2,6-dihydrobenzo[1:2-b,4:5-b'[difuran, isolated by filtration, washed successively with waterand methanol and dried.

A mixture of 1.6 g of this product, 1.38 K₂ CO₃ (anhyd), 2.2 gethoxyethyl bromoacetate and 25 ml of sulpholane was stirred and heatedat 110° C. for 2 hours. The mixture was cooled to ambient temperatureand added to 250 ml of stirred water. The product,3-phenyl-7(4-(ethoxyethoxycarbonylmethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran, was isolated by filtration, washed successively withwater and methanol and dried.

EXAMPLE 24

The procedure of Example 23 is repeated except that the 2.26 g of5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran was replaced by 2.84 g of5-hydroxy-2-oxo-3-(4-n-propoxyphenyl)-2,3-dihydrobenzo- furan. Theproduct,3-(4-hydroxyphenyl)-7-(4-n-propoxyphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran, was isolated as in Example 23.

A mixture of 1.86 g of this product, 1.38 g K₂ CO₃ (anhyd), 2.2 gethoxyethyl bromoacetate and 25 ml of sulpholane was stirred an heatedat 110° C. for 21/2 hours. After cooling to ambient temperature, themixture was added to 250 ml of water. The product,3-(4-n-propoxyphenyl)-7-(4-(ethoxyethoxycarbonylmethoxy)phenyl)-2,6dioxo-2,6-dihdyrobenzo[1:2-b,4:5-b'[difuran, was isolated by filtration, washed successively withwater and methanol and dried.

When applied to polyester materials from aqueous dispersion it givesbright bluish-red shades with good build up, good heat and lightfastness and good wet fastness.

EXAMPLE 25

The procedure of Example 1 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 4.8 g of4-amino-3-ethylphenyltartronic acid. The product,3-(4-aminophenyl)-7-(4-amino-3-ethylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran, dissolves in pyridine to give a blue shade having anabsorption maximum at 657 nm.

When a 50/50 mixture of his product and that of Example 1 was applied topolyester materials from aqueous dispersions it gave bright blue shadeswith good build up and good heat and wet fastness.

EXAMPLE 26

The procedure of Example 1 was repeated except that the 2.84 g of5-hydroxy-2-oxo-3-(4-acetylaminophenyl)-2,3-dihydrobenzo- furan wasreplaced by 3.0 g of5-hydroxy-2-oxo-3-(4-acetylamino-3-methylphenyl)-2,3-dihydrobenzofuran.The product,3,7-di(3-methyl-4-aminophenyl)-2,6-dioxo-2,6-dihdyrobenzo[1:2-b,4:5-b'[difuran, dissolves in pyridine to give a blue solution having aabsorption maximum at 660 nm.

When applied to polyester textile materials it gives bright blue shadeswith good heat fastness and good fastness to wash treatments.

EXAMPLE 27

The procedure of Example 8 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 4.4 g of4-amino-3,5-dimethylphenyltartronic acid to give3-phenyl-7-(4-amino-3,5-dimethylphenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran. This dissolves in chloroform to give a reddish-blueshade having an absorption maximum at 580 nm.

When applied to polyester materials it builds up to give navy blueshades with good heat and wet fastness.

EXAMPLE 28

The procedure of Example 8 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 4.6 g of4-amino-3-ethylphenyltartronic acid to give3-phenyl-7-(3-ethyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran. This dissolves in chloroform to give a reddish-blueshade having an absorption maximum at 568 nm.

When applied to polyester materials it builds up to give navy blueshades with good heat and wet fastness.

EXAMPLE 29

The procedure of Example 8 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 4.7 g of4-amino-3-n-propylphenyltartronic acid to give3-phenyl-7-(3-n-propyl-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran. This dissolves in chloroform to give a reddish-blueshade having an absorption maximum at 568 nm.

When applied to polyester materials it builds up to give navy blueshades with good heat and wet fastness.

EXAMPLE 30

The procedure of Example 8 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 4.5 g of4-amino-3-methoxyphenyltartronic acid to give3-phenyl-7-(3-methoxy-4-aminophenyl)-2,6-dioxo-2,6-dihdyrobenzo[1:2-b,4:5-b'[difuran. This dissolves in chloroform to give a reddish-blueshade having an absorption maximum at 600 nm.

When applied to polyester materials it builds up to give navy blueshades with good heat and wet fastness.

EXAMPLE 31

the procedure of Example 8 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 5.3 g of4-amino-3-ethoxyphenyltartronic acid to give3-phenyl-7-(3-ethoxy-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b,4:5-b'[difuran. This dissolves in chloroform to give a reddish-blueshade having an absorption maximum at 600 nm.

When applied to polyester materials it builds up to give navy blueshades with good heat and wet fastness.

EXAMPLE 32

The procedure of Example 8 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 5.5 g of4-amino-3-n-propoxyphenyltartronic acid to give3-phenyl-7-(3-n-propoxy-4-aminophenyl)-2,6-dioxo-2,6-dihydrobenzo 1:2-b,4:5-b'[difuran. This dissolves in chloroform to give a reddish-blueshade having an absorption maximum at 605 nm.

When applied to polyester materials it builds up to give navy blueshades with good heat and wet fastness.

EXAMPLE 33

The procedure of Example 8 was repeated except that the 4.8 g of4-amino-3-methylphenyltartronic acid was replaced by 5.0 g of3-methyl-4-N-ethylaminophenyltartronic acid to give3-phenyl-7-(3-methyl-4-N-ethylaminophenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b,4:5-b']difuran. This dissolves in chloroform to give a reddish-blueshade having an absorption maximum at 620 nm.

When applied to polyester materials it builds up to give navy blueshades with good heat and wet fastness.

The dyes identified in Tables 4 and 5 were prepared by the method ofExample 1 using equivalent amounts of the substituted mandelic acid##STR13## in place of the 4-acetylaminomandelic acid and of thesubstituted phenyltartronic acid ##STR14## in place of4-amino-3-methylphenyltartronic acid. In the case of the substitutedmandelic acids in which R¹ and R² are H or R⁶ is NH₂, the amino groupwas protected with an acetyl group which was subsequently removed byacid hydrolysis as described in Example 1.

In Table 4 the dyes correspond to Formula VII in which X¹, X², R⁵ and R⁸are all H and Z¹ and Z² are both O.

                                      TABLE 4                                     __________________________________________________________________________    Ex                                                                              R.sup.6    R.sup.1  R.sup.2                                                                              R.sup.4                                                                            R.sup.7                                                                            λmax/Shade                      __________________________________________________________________________    34                                                                              NHCH.sub.3 H        H      H    H    Mid Blue                               35                                                                              N(CH.sub.3).sub.2                                                                        CH.sub.3 CH.sub.3                                                                             H    H    Turquoise                              36                                                                              NHCH(CH.sub.3).sub.2                                                                     H        H      H    H    Mid Blue                               37                                                                              N(C.sub.2 H.sub.5).sub.2                                                                 H        H      H    H    Greenishblue                           38                                                                              NHEtCOOEt  C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      H    H     "                                     39                                                                              NHEtCOOMe  H        H      H    H    656                                    40                                                                              NHEtCOOEt  H        H      H    H    Mid Blue                               41                                                                              N(C.sub.2 H.sub.5).sub.2                                                                 EtCOOEtOMe                                                                             as R.sup.1                                                                           H    H    701                                    42                                                                              NHEtCOOEtOMe                                                                             H        H      H    H    Mid Blue                               43                                                                              N(C.sub.2 H.sub.5).sub.2                                                                 EtCOOMe  as R.sup.1                                                                           H    H    688                                    44                                                                              N(EtCOOMe).sub.2                                                                         H        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                           H    655                                    45                                                                              NH.sub.2   C.sub.2 H.sub.5                                                                        EtCOOEt                                                                              H    H    Greenishblue                           46                                                                              NHCH.sub.2 Ph                                                                            H        H      H    H    Mid blue                               47                                                                              N-morpholino                                                                             CH(CH.sub.3).sub.2                                                                     EtCOOMe                                                                              H    H    672                                    48                                                                              N(C.sub.2 H.sub.4 OH).sub.2                                                              EtCOOMe  as R.sup.1                                                                           H    H    Greenishblue                           49                                                                              N(EtOCOMe).sub.2                                                                         EtCOOMe  as R.sup.1                                                                           H    H     "                                     50                                                                              N-piperidino                                                                             EtCOOEtOMe                                                                             as R.sup.1                                                                           H    H    684                                    51                                                                              N-piperidino                                                                             EtCOOMe  as R.sup.1                                                                           H    H    677                                    52                                                                               ##STR15## C.sub.2 H.sub.4 CN                                                                     EtCOOMe                                                                              H    H    Greenishblue                           53                                                                              NHC.sub.2 H.sub.4 CN                                                                     C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      H    H     "                                     54                                                                              N(C.sub.2 H.sub.4 OH).sub.2                                                              H        H      H    H     "                                     55                                                                              NHCH(CH.sub.3).sub.2                                                                     C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                       H   H    705                                    56                                                                              NH.sub.2   H        H      CH.sub.3                                                                           Cl   656                                    57                                                                              N-morpholino                                                                             CH(CH.sub.3)C.sub.2 H.sub.5                                                            H      CH.sub.3                                                                           H    675                                    58                                                                              N-morpholino                                                                             CH(CH.sub.3).sub.2                                                                     H      CH.sub.3                                                                           H    670                                    59                                                                              N-morpholino                                                                             CH(CH.sub.3).sub.2                                                                     H      H    H    674                                    60                                                                              N-morpholino                                                                             CH(CH.sub.3)C.sub.2 H.sub.5                                                            H      H    H    676                                    61                                                                              NHEtCOOEt  EtCOOEt  H      CH.sub.3                                                                           H    650                                    62                                                                              NHEtCOOMe  CH(CH.sub.3).sub.2                                                                     H      H    H    688                                    63                                                                              NHC.sub.2 H.sub.5                                                                        CH(CH.sub.3)C.sub.2 H.sub.5                                                            H      CH.sub.3                                                                           CH.sub.3                                                                           689                                    64                                                                              NHCH(CH.sub.3).sub.2                                                                     CH(CH.sub.3)C.sub.2 H.sub.5                                                            H      H    H    698                                    65                                                                              NHC.sub.6 H.sub.13                                                                       CH(CH.sub.3).sub.2                                                                     H      H    H    693                                    66                                                                              NHC.sub.2 H.sub.5                                                                        CH(CH.sub.3).sub.2                                                                     H      CH.sub.3                                                                           CH.sub.3                                                                           691                                    67                                                                              NH[CH]     [ CH]    H      CH.sub.3                                                                           H    Turquoise                              68                                                                              NHEtCOOMe  CH(CH.sub.3)C.sub.2 H.sub.5                                                            H      H    H    688                                    69                                                                              NH[CH]     H        H      H    H    Mid Blue                               70                                                                              NH(s-C.sub.4 H.sub.9)                                                                    H                                                                s-C.sub.4 H.sub.9                                                               CH.sub.3   C.sub.2 H.sub.5                                                                        695                                                     71                                                                              N(C.sub.2 H.sub.5).sub.2                                                                 H        H      CH.sub.3                                                                           H    674                                    72                                                                              NHC.sub.2 H.sub.5                                                                        H        H      CH.sub.3                                                                           CH.sub.3                                                                           Greenishblue                           73                                                                              NHCH(CH.sub.3 C.sub.2 H.sub.5                                                            C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      H    H    Turquoise                              74                                                                              N(C.sub.2 H.sub.5).sub.2                                                                 CH(CH.sub.3).sub.2                                                                     H      CH.sub.3                                                                           H     "                                     75                                                                              NH[CH]-pCH.sub.3                                                                         C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      H    H     "                                     76                                                                              NHCH(CH.sub.3).sub.2                                                                     C.sub.2 H.sub.5                                                                        CH.sub.2 -Ph                                                                         H    H     "                                     77                                                                               ##STR16## C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      H    CH.sub.3                                                                           Turquoise                              78                                                                              N(CH.sub.3).sub.2                                                                        H        H      H    H    Greenishblue                           79                                                                              NH.sub.2   C.sub.2 H.sub.5                                                                        CH.sub.2 -Ph                                                                         H    H     "                                     80                                                                              NHCH(CH.sub.3).sub.2                                                                     CH(CH.sub.3).sub.2                                                                     H      CH.sub.3                                                                           H    689                                    81                                                                              NHEtCOOMe  C.sub.2 H.sub.5                                                                        EtCOOMe                                                                              H    H    Greenishblue                           82                                                                              NH.sub.2   H        H      OC.sub.2 H.sub.5                                                                   H    664                                    83                                                                              N(CH.sub.3).sub.2                                                                        CH(CH.sub.3).sub.2                                                                     H      H    H    Turquoise                              84                                                                              NHC.sub.6 H.sub.13                                                                       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      H    H     "                                     85                                                                              NH.sub.2   C.sub.4 H.sub.9                                                                        C.sub.3 H.sub.6 -Ph                                                                  H    H     "                                     __________________________________________________________________________     In Table 4 and the subsequent tables:                                         NH[CH]-pCH.sub.3 = 4methylcyclohexylamino-                                    [CH] = cyclohexyl                                                              EtCOOEtOMe = C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCH.sub.3              EtCOOEt = C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                            OEtOEt = OC.sub.2 H.sub.5 OC.sub.2 H.sub.5                                    Ph = phenyl                                                                   EtCOOMe = C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                   OEtMe = OC.sub.2 H.sub.4 OCH.sub.3                                            OEtOCOMe = OC.sub.2 H.sub.5 OCOCH.sub.3                                  

In Table 5 the dyes correspond to Formula VII in which X¹, X², R⁵, R⁷and R⁸ are all H and Z¹ and Z² are both O.

                  TABLE 5                                                         ______________________________________                                                                                max/                                  Ex  R.sup.6  R.sup.1    R.sup.2   R.sup.4                                                                             Shade                                 ______________________________________                                        86  --OCH.sub.3                                                                            --EtCOOMe  --C.sub.2 H.sub.4 CN                                                                    --H   Reddish-                                                                      blue                                  87  --OCH.sub.3                                                                            --EtCOOMe  --C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                     --H   Reddish-                                                                      blue                                  88  --H      --C.sub.2 H.sub.5                                                                        --H       --H   607                                   89  --OC.sub.3 H.sub.7                                                                     --CH.sub.3 --CH.sub.3                                                                              --H   Navy                                  90  --H      --CH.sub.3 --H       --H   Reddish-                                                                      blue                                  91  --H      --H        --H       --H   Reddish-                                                                      blue                                  92  --OC.sub.3 H.sub.7                                                                     --EtCOOMe  --C.sub.2 H.sub.4 CN                                                                    --H   Navy                                  93  --H      --C.sub.2 H.sub.5                                                                        --C.sub.2 H.sub.4 OH                                                                    --H   647                                   94  --H      --C.sub.2 H.sub.5                                                                        --EtOCOMe --H   Navy                                  95  --CH.sub.3                                                                             --H        --H       --CH.sub.3                                                                          Reddish-                                                                      blue                                  96  --H      --CH.sub.3 --CH.sub.3                                                                              --H   Reddish-                                                                      blue                                  97  --H      --EtCOOEt  --H       --H   Reddish-                                                                      blue                                  98  --H      --C.sub.4 H.sub.9                                                                        --C.sub.3 H.sub.6 --Ph                                                                  --H   Navy                                  ______________________________________                                    

Further dyes in accordance with Formula VII which can be made by thesame process as the dyes in Tables 4 and 5 are shown in Tables 6, 7 and8. In the dyes shown in Table 6 X¹, X², R⁵, R⁷ and R⁸ are all H and Z¹and Z² are both O.

                  TABLE 6                                                         ______________________________________                                        Example                                                                              R.sup.6   R.sup.4      R.sup.1                                                                            R.sup.2                                    ______________________________________                                         99    --H       --Cl         --H  --H                                        100    --H       --C.sub.4 H.sub.9                                                                          --H  --H                                        101    --H       --CH.sub.3   --H  --C.sub.2 H.sub.4 OH                       102    --H       --CH.sub.3   --H  --C.sub.2 H.sub.4 CN                       103    --H       --CH.sub.3   --H  --C.sub.2 H.sub.4 Cl                       104    --H       --C.sub.2 H.sub.5                                                                          --H  --EtOCOMe                                  105    --H       --C.sub.2 H.sub.5                                                                          --H  --EtCOOMe                                  106    --H       --CH.sub.3   --H  --C.sub.2 H.sub.4 OCH.sub.3                107    --H       --CH.sub.3   --H  --C.sub.3 H.sub.6 --Ph                     108    --H       --OC.sub.4 H.sub.9                                                                         --H  --H                                        109    --H       --OEtOEt     --H  --H                                        110    --H       --OEtOCOMe   --H  --H                                        111    --H       --OC.sub.2 H.sub.4 CN                                                                      --H  --H                                        112    --H       --OCH.sub.3  --H  --C.sub.2 H.sub.4 CN                       113    -- H      --OCH.sub.3  --H  --EtOCOMe                                  114    --H       --Br         --H  --C.sub.2 H.sub.4 OCH.sub.3                115    --CH.sub.3                                                                              --CH.sub.3   --H  --H                                        116    --C.sub.2 H.sub.5                                                                       --CH.sub.3   --H  --C.sub.2 H.sub.5                          117    --Cl      --CH.sub.3   --H  --C.sub.3 H.sub.7                          118    --OCH.sub.3                                                                             --H          --H  --H                                        119    --OC.sub.4 H.sub.9                                                                      --H          --H  --H                                        120    --H       --H          --H  --C.sub.6 H.sub.13                         121    --H       --CH.sub.3   --H  --C.sub.6 H.sub.13                         122    --OCH.sub.3                                                                             --H          --H  --C.sub.8 H.sub.17                         ______________________________________                                    

In the dyes shown in Table 7 X¹, X², R⁵ and R⁸ are all H and Z¹ and Z²are both O.

                                      TABLE 7                                     __________________________________________________________________________    Ex R.sup.6  R.sup.7                                                                              R.sup.4                                                                           R.sup.1 R.sup.2                                        __________________________________________________________________________    123                                                                              --NH.sub.2                                                                             --Cl   --CH.sub.3                                                                        --H     --C.sub.2 H.sub.5                              124                                                                              --NH.sub.2                                                                             --Br   --H --H     --H                                            125                                                                              --NH.sub.2                                                                             --OEtOMe                                                                             --H --C.sub.2 H.sub.5                                                                     --C.sub.2 H.sub.5                              126                                                                              --NH.sub.2                                                                             --C.sub.3 H.sub.7                                                                    --H --H     --H                                            127                                                                              --NH.sub.2                                                                             --C.sub.2 H.sub.5                                                                    --CH.sub.3                                                                        --H     --C.sub.2 H.sub.4 CN                           128                                                                              --OC.sub.3 H.sub.7                                                                     --H    --H --C.sub.2 H.sub.4 CN                                                                  --EtCOOMe                                      129                                                                              --N(C.sub.2 H.sub.5).sub.2                                                             --H    --H --EtCOOMe                                                                             --EtCOOMe                                      130                                                                              --N(C.sub.2 H.sub.5 OH).sub.2                                                          --CH.sub.3                                                                           --H --C.sub.2 H.sub.5                                                                     --C.sub.3 H.sub.7                              131                                                                              --H      --H    --H --C.sub.2 H.sub.5                                                                     --C.sub.2 H.sub.5                              132                                                                              --CH.sub.3                                                                             --H    --H --C.sub.2 H.sub.5                                                                     --C.sub.2 H.sub.5 OH                           133                                                                              --OCH.sub.3                                                                            --Cl   --H --C.sub.2 H.sub.5                                                                     --C.sub.2 H.sub.5                              134                                                                              --N(C.sub.2 H.sub.5).sub.2                                                             --H    --CH.sub.3                                                                        --H     --EtOCOMe                                      135                                                                              --NHC.sub.2 H.sub.5                                                                    --CH.sub.3                                                                           --H --C.sub.2 H.sub.4 OH                                                                  --C.sub.2 H.sub.5                              136                                                                              --NHC.sub.2 H.sub.4 OH                                                                 --CH.sub.3                                                                           --CH.sub.3                                                                        --H     --C.sub.2 H.sub.4 CN                           137                                                                              --NH.sub.2                                                                             --H    --CH.sub.3                                                                        --H     --Ph                                           138                                                                              --NHC.sub.2 H.sub.5 Y                                                                  --H    --H --H                                                    4-Cl--Ph--                                                                    __________________________________________________________________________

In the dyes shown in Table 8 X¹ and X² are both H and Z¹ and Z² are bothO.

                  TABLE 8                                                         ______________________________________                                        Ex   R.sup.7                                                                              R.sup.6  R.sup.8                                                                             R.sup.4                                                                             R.sup.5                                                                             R.sup.1                                                                              R.sup.2                         ______________________________________                                        139  --H    --NH.sub.2                                                                             --H   --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H    --H                             140  --Cl   --OC.sub.3 H.sub.7                                                                     --Cl  --H   --H   --H    --H                             141  --Cl   --NH.sub.2                                                                             --Cl  --H   --H   --C.sub.2 H.sub.5                                                                    --H                             142  --H    --H      --H   --C.sub.2 H.sub.5                                                                   --H   --H    --H                             ______________________________________                                    

We claim:
 1. A process for the preparation of a polycyclic dye ofFormula I: ##STR17## by reacting a phenyltartronic acid of Formula II:##STR18## wherein: W is --NR¹ R² or --OR³ ;R³ is H or C₁₋₂₀ -alkyl,C₂₋₂₀ -alkenyl, C₄₋₈ -cycloalkyl or phenyl-C₁₋₄ -alkylene group each ofwhich is unsubstituted or is substituted by a group selected from alkyl,alkoxy, nitro, halogen, alkoxyalkoxy, cyclohexyl, phenyl, diphenyl,hydroxy, alkylcarbonyl, alkoxycarbonyl, alkoxyalkoxy carbonyl,alkoxycarbonyloxy, alkoxyalkoxycarbonyloxy, alkylcarbonyloxy, cyano andamino in which each alkyl is C₁₋₄ -alkyl; R¹ & R² are each independentlyH or C₁₋₂₀ -alkyl, C₂₋₂₀ -alkenyl, C₄₋₈ -cycloalkyl, phenyl-C₁₋₄-alkylene or phenyl group each of which is unsubstituted or issubstituted by a group selected from alkyl, alkoxy, nitro halogen,alkoxyalkoxy, cyclohexyl, phenyl, diphenyl, hydroxy, alkylcarbonyl,alkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyloxy,alkoxyalkoxycarbonyloxy, alkylcarbonyloxy, cyano and amino in which eachalkyl is C₁₋₄ -alkyl; or R¹ & R² together with the nitrogen atom towhich they are attached from a piperidino or morpholino group; or R¹ orR² together with the nitrogen atom and the adjacent carbon atom of RingB form a tetrahydroquinolinyl group; and Ring B is unsubstituted, apartfrom the group W, or is substituted by from one or two further groupsselected from alkyl; alkenyl; alkoxy; alkoxyalkoxy; alkoxycarbonyalkoxy;alkoxyalkoxycarbonyl alkoxy; alkylcarbonyloxyalkoxy; cyanoalkoxy;hydroxyalkoxy; chlorine; bromine; hydroxy; alkylthio; arylthio; aryloxy;alkylcarbonyl and alkylsulphonyl; in which the alkyl or alkenyl containsup to 4 carbon atoms and the aryl is phenyl;with either (a) a compoundof Formula III: ##STR19## wherein, Z¹ & Z² are each --O--; X¹ & X² areeach independently selected from H, halogen, cyano, alkyl, aryl,carbamoyl, sulphamoyl, COOH and carboxylic acid ester; & Ring A isunsubstituted or is substituted by from one to three groups selectedfrom alkyl; alkenyl; alkoxy; alkoxyalkoxy; alkoxycarbonylalkoxy;alkoxyalkoxycarbonylalkoxy; alkylcarbonyloxyalkoxy; cyanoalkoxy;hydroxyalkoxy; chlorine; bromine; hydroxy; akylthio; arylthio; aryloxy;alkylcarbonyl and alkylsulphonyl; in which the alkyl or alkenyl containsup to 4 carbon atoms and the aryl is phenyl; NHCOC₁₋₄ -alkyl; --NHSO₂C₁₋₄ -alkyl; NR¹ R² and OR³, wherein R¹, R² and R³ are as hereinbeforedefined;or (b) a compound of Formula IV: ##STR20## wherein Z¹, Z², X¹and X² are as hereinbefore defined; and oxidation of the intermediatecompound to dehydrogenate the peripheral heterocyclic rings.